Method of preparing highly active nickel catalysts and catalysts prepared by said method

Abstract

{PG,1 The instant invention relates to a method for preparing high activity supported nickel catalysts. The method comprises the deposition of nickel nitrate on a carrier, typically an inert inorganic refractory oxide, by techniques known in the art followed by careful heating to a temperature of between 100{20 {0 to 270{20 {0 C., avoiding any excursions into temperatures beyond the stated maxima, in a flowing nonreactive gas atmosphere for a time sufficient to convert substantially all of the nickel nitrate into nickel oxide. When using an H{HD 2 {L containing atmosphere the maximum temperature is 220{20 {0 C. The supported nickel oxide resulting from the above procedure is then reduced to a supported nickel metal catalyst in a reducing atmosphere at a temperature ranging from about 230{20 {0 C. to 400{20 {0 C.

What is claimed is: 
     
       1. A process for the preparation of a supported nickel catalyst comprising the following steps: (a) depositing nickel nitrate on an inert inorganic refractory oxide support or carbon;   (b) decomposing the nickel nitrate on the support to nickel oxide at a temperature of from 100° to 270° C. in a flowing gaseous atmosphere which gaseous atmosphere is characterized as not decomposing at the temperature utilized and does not contain hydrogen, said nickel nitrate decomposition being conducted essentially to completion as indicated by the cessation of the evolution of nitrogen oxides;   (c) reducing the nickel oxide on the support of step (b) to nickel metal on the support under a reducing atmosphere at a temperature of from 230° to 350° C.   
     
     
       2. The process of claim 1 wherein the support is selected from the group consisting of alumina, silica, silica-alumina, magnesia, zirconia, titania, zirconium titanate. 
     
     
       3. The process of claim 2 wherein the support is alumina. 
     
     
       4. The process of claim 1 wherein the nickel nitrate is deposited on the support from solution. 
     
     
       5. The process of claim 4 wherein the nickel nitrate solution is aqueous. 
     
     
       6. The process of claim 1 wherein the decomposition temperature of step (b) ranges from 150° to 230° C. 
     
     
       7. The process of claim 1 wherein the decomposition temperature of step (b) ranges from 200° to 230° C. 
     
     
       8. The process of claim 1 wherein the reducing atmosphere of step (c) is a hydrogen containing atmosphere. 
     
     
       9. A supported nickel catalyst prepared by the process of the following steps: (a) depositing nickel nitrate on an inert inorganic refractory oxide support or carbon;   (b) decomposing the nickel nitrate on the support to nickel oxide at a temperature of from 100° to 220° C. in a flowing hydrogen containing atmosphere, said nickel nitrate decomposition being conducted essentially to completion as indicated by the cessation of the evolution of nitrogen oxides; and   (c) reducing the nickel oxide on the support from step (b) to nickel metal on the support under a reducing atmosphere at a temperature of from 230° to 400° C.   
     
     
       10. The product prepared by the process of claim 9 wherein the nickel nitrate is deposited on the support from solution. 
     
     
       11. The product prepared by the process of claim 10 wherein the nickel nitrate solution is aqueous. 
     
     
       12. The product prepared by the process of claim 9 wherein the supports are selected from the group consisting of alumina, silica, silica-alumina, magnesia, zirconia, titania, zirconium titanate, zeolites and mixtures thereof. 
     
     
       13. The product prepared by the process of claim 12 wherein the support is alumina. 
     
     
       14. The product prepared by the process of claim 9 wherein the decomposition temperature of step (b) ranges from 200° to 220° C. 
     
     
       15. The product prepared by the process of claim 13 wherein the alumina has a surface area of from 20 to 700 m 2  /g determined by nitrogen adsorption at 77° K. 
     
     
       16. The product prepared by the process of claim 9 wherein the reducing atmosphere of step (c) is hydrogen. 
     
     
       17. The product prepared by the process of claim 9 wherein the temperture of reduction in step (c) is 230° to 350° C. 
     
     
       18. The product prepared by the process of claim 16 wherein the temperature of reduction of step (c) is 230°-300° C. 
     
     
       19. The process of claim 1 wherein the temperature of reduction of step (c) is 230°-300° C. 
     
     
       20. The process of claim 1 wherein the nickel metal loading of the catalyst ranges from 0.1-50 wt. %. 
     
     
       21. The product prepared by the process of claim 16 wherein the nickel metal loading of the catalyst ranges from 0.1-50 wt. %. 
     
     
       22. The process of claim 1 wherein the flow rate during decomposition step (b) is at least 10 cc/min/gram. 
     
     
       23. The product prepared by the process of claim 9 wherein the flow rate during decomposition step (b) is at least 10 cc/min/gram. 
     
     
       24. The product prepared by the process of claim 9 wherein the hydrogen containing atmosphere of step (b) is 17% H 2  in nitrogen.